Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
  • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
  • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
  • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
  • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/47—Condensation polymers of aldehydes or ketones
  • D21H17/48—Condensation polymers of aldehydes or ketones with phenols

Definitions

• ABSTRACT Subject of the invention is a process for the manufacture of water-dilutable, aqueous dispersions, containing emulsifiers and protective colloids, of thermosetting reaction products of monohydroxybenzene compounds or mixtures of monohydroxybenzene compounds with formaldehyde in water, wherein these components are reacted with one another in water in the presence of basic nitrogen compounds, whilst warming, in a three-stage process.
• the present invention relates to a process for the manufacture of water dilutable aqueous dispersions containing emulsifiers and protective colloids, of thermosetting reaction products of monohydroxybenzene compounds or mixtures of monohydroxybenzene compounds with formaldehyde in water, these components being caused to react with one another in water in the presence of basic nitrogen compounds, whilst warming.
• thermosetting phenolic resins Numerous proposals for the manufacture of aqueous dispersions of thermosetting phenolic resins have already been described in the relevant literature. However, the proposals made hitherto have not proved successful in practice so that dispersions of thermosetting phenol-formaldehyde resol resins are not yet customary commercially available articles.
• Prior Art German Patent Specification No. 838,215 describes a process for the manufacture of stable, aqueous dispersions of soluble phenolic resins which is characterised in that solutions of the phenolic resins in organic solvents are dispersed in water with the aid of soap-like emulsifiers and of polyvinyl alcohol or its water-soluble derivatives.
• the organic solvents also have to be evaporated so that expensive equipment must be used in order to meet the environmental standards of industrial hygiene.
• German Offenlegungsschrift No. 1,745,192 describes a process for the manufacture of aqueous emulsions of phenol-formaldehyde resol resins for impregnating fibrous substances, such as paper, in which the phenol is caused to react with an excess of formaldehyde in water in the presence of organic bases containing amino groups, and which is characterised in that the reaction between phenol and formaldehyde is carried out in an aqueous medium in which orgainc nitrogen bases with tertiary and primary and/or secondary amino groups are present, the ratio between the tertiary amino groups on the one hand and the primary and/or secondary amino groups on the other being between 1:25 and 1:1.5.
• the disadvantage of these aqueous emulsions is that they still contain ions and that therefore they cannot be used to achieve the optimum properties of the impregnated fibrous substances, due to the interfering ion content.
• German Offenlegungsschrift No. 1,595,038 describes a process for the manufacture of an emulsion of thermosetting low molecular reaction product of a monohydroxybenzene compound or of a mixture of monohydroxybenzene compounds and formaldehyde in water, wherein the compounds mentioned are reacted with one another in water in the presence of a basic substance, using an amide with a long carbon chain as a plasticiser, and which is characterised in that the amide used is oleylamide.
• These emulsions have the disadvantages already explained above since, being reaction products of low condensation, they still contain considerable proportions of free phenol and/of formaldehyde.
• the emulsified phenolformaldehyde resin obtained according to this process is so brittle that it can only be used together with an additional plasticiser, which can result in further disadvantages due to migration of the plasticiser.
• German Offenlegungsschrift No. 2,034,136 describes a phenol-aldehyde condensation product which is characterised in that it is obtained by reaction, at about 60 to C, of i a. one mol of a monohydric phenol with at least two hydrogen atoms which are reactive towards an aldehyde and b. at least one mol of an aldehyde of the general formula O in which 11 is an integer CnH2n+r- H from O to 10,
• the phenol-aldehyde condensation product described there liquefied by warming, can be emulsified in an aqueous solution which contains 1 percent of hydroxyethylcellulose and a non-ionic surface-active agent Triton X as a 1 percent strength solution, using a special stirrer.
• the resin used contains zinc acetate as the ionic compound and furthermore the resin additionally contains 12 percent of volatile compounds so that this resin again suffers from the disadvantages mentioned above;
• thermosetting aqueous solutions of phenol-formaldehyde resins can only be stored for a few weeks since they condense further over the course of time and hence lose their solubility in water.
• these solutions must necessarily still contain considerable proportions of free phenol and free formaldehyde.
• Some types of these phenolic resin solutions are additionally alkaline and therefore contain ions.
• the phenol-formaldehyde resins contained in the dispersions according to the invention are present in a stable form so that these dispersions can be stored practicallyindefinitely, which after setting can be converted into dispersions by simply stirring. Furthermore, the proportion of undesired volatile constituents is lower by powers of ten than in the known phenolic resin solutions. Furthermore, the phenol-formaldehyde resins contained in the dispersions manufactured according to the invention can be manufactured extremely economically since the starting substances are converted to the resin to the extent of practically 100 percent.
• the dispersions according to the invention have the great advantage that they can also entirely replace the previous phenolic resin solutions in which the phenolic resin is present dissolved in an organic solvent.
• the previously known phenolic resin solutions also still contain free phenol, free formaldehyde and organic solvent, which in general also has a toxic effect.
• considerable advantages in industrial hygiene result from the replacement of these phenolic resin solutions.
• considerable economic advantages also result since the explosion-proof processing installations and solvent recovery installations previously required are unnecessary.
• the use of the dispersions manufactured according to the invention is substantially simpler than the use of phenolic resins dissolved in the solvent, since the substrates treated with the dispersions manufactured according to the invention are in general only subjected to a physical drying process and are then in the form of finished goods or semifinished goods which can be processed further.
• the Japanese Displayed Specification Sho 46-27256 discloses a process for the manufacture of emulsions of phenolic resins characterized by reacting (a) phenol -100 parts by weight), (b) low molecular amino compounds reactive with formaldehyde or xylene (0-90 parts by weight) and (c) aldehyde or similar reacting compounds (0.3 mols relative to 1 mol of the sum of (a) and ([7), reduced to aldehyde contents) in such a manner that either the components are reacted in the presence of polyvinylalcohol until a product is obtained, which is not soluble in aqueous solutions of pH below I l, and thereafter adding an emulsifier at once.
• the emulsifier may be added only after the phenolic resin has been obtained. Therefore it has been surprising that in the process of the present invention a nonionic emulsifier is already added during the manufacture of the phenolic resin. Using the same non-ionic emulsifier no water-dilutable emulsions of the type water in resin can be obtained according to the method of the Japanese patent specification, while according to the method of the present invention always waterdilutable dispersions of the type phenolic resin-in-water are obtained. That is even the same emulsifier does not lead to water-dilutable phenolic resin dispersions, if the known method of the Japanese patent application is employed for the production. For this reason the result of the method according to the present invention is rather surprising. The advance over this known working method has been proven to the end of this specifica tion by comparison tests.
• the subject of the invention is a process for the manufacture of water-dilutable, aqueous dispersions containing emulsifiers and protective colloids of thermosetting reaction products of monohydroxy benzene compounds or mixtures of monohydroxybenzene compounds with formaldehyde in water, wherein these components are reacted with one another in water in the presence of basic nitrogen compounds, whilst warming, characterized in that, in a two-stage process first a mixture (A) consisting of: one or more substituted phenols, which have at least one but no more than 2 carbon atoms in the phenolic ring being reactive with formaldehyde, and
• phenol which has 3 carbon atoms in the phenolic ring being reactive with formaldehyde
• a mixture (B) consisting of: one or more substituted phenols, which have at least one but no more than 2 carbon atoms in the phenolic ring being reactive with formaldehyde, and
• a mixture (C) consisting of: one or more substituted phenols which have at least one but no more than 2 carbon atoms in the phenolic ring being reactive with formaldehyde, and
• phenol which has 3 carbon atoms in the phenolic ring being reactive with formaldehyde
• the mixture A, B or C being employed in such ratios that the average functionality of the sum of the phenolic compounds in the mixture A, B or C relative to formaldehyde is between 2.1 and 2.8, and the amount of formaldehyde being so chosen that the molar ratio of the total sum of added formaldehyde to the sum of the phenolic compounds in the mixture A, B or C is between 0.9 and 1.5 l
• the basic nitrogen compound being employed in amounts of 5 to 50 mol percent relative to the total weight of phenols in the mixture A, B or C, and warmed for reaction until a sample of the condensation product withdrawn has a B-time of 6 minutes at
• a further object of the invention is a method for the production of water-dilutable, aqueous dispersions containing emulsifiers and protective colloids of thermosetting reaction products of mixtures of monohydroxybenzene compounds and formaldehyde in water, whereby these components are made to react by heating in the presence of basic nitrogen compounds, characterized in that in a three-step process 1.
• a mixture (A) consisting of: one or more substituted phenols having at least one but no more than 2 carbon atoms in the phenolic ring which are reactive with formaldehyde, and
• phenol (which has 3 carbon atoms in the phenolic ring being reactive with formaldehyde) is made by reacting in the first step an aralkylphenol solution in phenol produced by reacting 1 mol of phenol with l mol of styrene or styrene derivative in excess phenol as the solvent by heating, whereby about 2 to 5 percent by weight of oxalic acid, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least 95 percent by weight of the styrene derivative employed is present in reacted form,
• a mixture (B) consisting of: one or more substituted phenols having at least 1 but no morev than 2 carbon atoms in the phenolic ring which are reactive with formaldehyde, and
• one or more other substituted phenols having 3 carbon atoms in the ring which are reactive with formaldehyde is made by reacting in the first step an aralkylphenol solution in phenol produced by reacting l mol of phenol with 1 mol of styrene or styrene derivative in excess phenol as the solvent by heating. whereby about 2 to 5 percent by weight of oxalic acid, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least 95 percent by weight of the styrene or styrene derivative employed is present in reacted form,
• a mixture (C) consisting of: one or more substituted phenols having at least 1 but no more than 2 carbon atoms in the phenolic ring which are reactive with formaldehyde, and
• phenol (which has 3 carbon atoms in the phenolic ring being reactive with formaldehyde) is made by reacting in the first step an aralkylphenol solution in phenol produced by reacting 1 mol of phenol with 1 mol ofstyrene or styrene derivative in excess phenol as the solvent by heating, whereby about 2 to 5 percent by weight of oxalic acid, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least percent by weight of the styrene or styrene derivative employed is present in reacted form, and
• the mixture A, B or C is reacted with formaldehyde or formaldehyde donors and basic nitrogen compounds selected from the group consisting of ammonia and/or primary or secondary amines, whereby the mixture A, B or C is employed in such amounts that the average functionality of the sum ofthese phenolic compounds of the mixture A, B or C to formaldehyde is between 2.l and 2.8 and the amount of formaldehyde is so chosen that the molar ratio of the total sum of added formaldehyde to the sum of phenolic compounds in the mixture A, B or C is between 0.9 and 1.5 l and wherein the basic nitrogen compound being employed in amounts of 5 to 50 mol percent, relative to the total weight of phenols in the mixture A, B or C is warmed until a sample ofthe condensation product withdrawn has a B-time of 6 15 minutes at 160C, the batch is cooled to below C and 3.
• the resulting water-in-phenolic resin dispersion (of a water-in-oil type) is mixed with water and protective colloid and agitated mechanically until a phase inversion of the dispersion takes place, so that a dispersion of the oil-in-water type is present, and the phenolic resin-in-water dispersion" is condensed further by warming until a withdrawn sample of the dispersion has a B-time of 30 seconds to 10 minutes at C, and the batch is subsequently cooled whilst stirring.
• the B-time or curing time is measured similarly to the test procedure 4 described on page 174 of the book Kunststoff-Praktikum (Practical Plastics) (Gaeteno DAlelio, Carl-Hanser- Verlag/Munich 1952), wherein 0.3 of resin is stirred, at the indicated temperature, in a bowl of diameter 2 cm and maximum depth 8 mm by means of a glass rod drawn out to a point until it cures, and the time required to achieve this is measured.
• thermosetting reaction products of monohydroxybenzene compounds or mixtures of monohydroxyben- Zene compounds with formaldehyde there are understood resinous condensates such as are known to experts under the name resols (compare Ullmanns Enzyklopadie der techn. Chemie, Verlag Urban 8!. Schwarzenberg, Munchen, Berlin, 1962, pages 459-467).
• ammonia and/or primary and/or secondary preference being given to the use of ammonia or of those amines which have a basicity equal to or greater than that of ammonia.
• Suitable substituted phenols are those which contain, as substituents, alkyl radicals with l-30 C atoms, cycloalkyl radicals with -10 atoms which can be of monocyclic or bicyclic structure, alkenyl radicals with 1-30 C atoms and/or cycloalkenyl radicals with 5-10 C atoms, which are again of monocyclic or bicyclic struc-.
• Halogen-substituted phenols and aryl-substituted phenols having an aromatic ring in the substituent are also suitable.
• Substituted phenols must beso chosen that they possess 1,2,3 or 4 substituents on the phenol nucleus but at least one carbon atom capable of reaction with formaldehyde must be present in the phenol ring, and that the speed of reaction of the substituted phenol with formaldehyde is 40 to 150 percent of the speed of reaction of the unsubstituted phenol (compare LA. Cohen and W.M. Jones; Journal of the American Chemical Society, year 85 (1963), page 3,402.
• the speed of reaction can also be determined by comparative measurement of the formaldehyde consumption as a function of the reaction time in molar solutions of the phenols which contain alkali).
• substituted phenols which contain 2 carbon atoms, capable of reacting with formaldehyde, in the phenol ring are preferred.
• Substituted phenols with 3 reactive positions in the phenol ring can be used individually or in minor amounts in mixtures.
• the following substituted phenols can be used for the present process: m-cresol, 3,4-, 3,5- and 2,5- dimethylphenol, m-ethylphenol,-m-propylphenol, m-nbutylphenol, p-tert.-butylphenol, 0- and/or p-, nand- /or iso-propenylphenol, 0' and/or p-allylphenol, ophenylphenol, p-phenylphenol, m-phenylphenol, 0- and/or p- 0:- and/or ,B-phenylethylphenol individually or as mixtures, 0- and/or p-aand/or B-phenylisopropylphenol, 0- and/or p-aand/or B-methylphenylethylphenol and also technical alkylation products of olefines and phenols, of which the manufacture has been described, for example, in British Patent No.
• 327, 382, page 5, lines 25-34, and 0- and/or paminophenols Preferably p-tert.-butylphenol, oand- /or p-a-and/or -BB-phenylethylphenol, individually or in mixture, 0- and/or p-aand/or--,B-phenylisopropylphenol, o-and/or paand/or -B-methylphenylethylphenol, and ethylene/phenol substituted phenol reaction products which boil at from 230to 260C, and of which substituted phenol reaction product 60 to 70 percent of which dissolves in an alkaline solution, as referred to in British Patent No. 327, 382 page 5, lines 25-34.
• formaldehyde or formaldehyde donors aqueous formaldehyde solutions, gaseous formaldehyde paraformaldehyde and hexamethylenetetramine.
• aqueous formaldehyde or paraformaldehyde are employed.
• the suitable primary or secondary amines include those organic substances which contain one or more primary amino groups or one or more secondary amino groups optionally both primary and secondary amino groupsand which are soluble in the reaction mixture and are preferably not'less basic than ammonia, which means that the pK value should be s 5 at 20C.
• NH- will in the subsequent text also be included amongst the primary amines.
• ammonia NH ethylamine, isobutylamine, tertiary butylamine, cyclohexylamine, ethanolamine, dimethylamine, diethylamine, diisopropylamine, diethanolamine, piperidine,methylpyrrolidine, morpholine, ethylenediamine, hexamethylenediamine. piperazine, diethylenetriamine, triethylenetetramine and guanidine.
• ammonia, dimethylamine, morpholine or diethanolamine are used.
• non-ionic emulsifiers which are compatible with phenolic resin it is possible to use: addition products of ethylene oxide to alkylphenols with one or more substituents, such as are described, for example, in the publication by Farbwerke Hoechst AG, Frankfurt/m, Hoe. 2825 TH/S, of November 1962, under the title Arkopal N-Marken (Arkopal N Grades), wherein 10-35 mols of ethylene oxide are added onto the alkylphenol in the manner of a polyether, as well as ethylene oxide adducts to polypropylene glycols of various chain lengths, such as have been described in the publication by Messrs. C. H. Erbsloh, Dusseldorf, under the title Pluronic.
• ethylene oxide addition products to natural resin acids such as, for example, abietic acid
• natural resin acids such as, for example, abietic acid
• ethylene oxide addition products to natural resin acids are suitable, such as have been described in the publication by Wegriken Bayer AG, Leverkusen (Le 681(N) of January 1968) under the title Emulsifier U.
• non-ionic agents it is furthermore possible to use polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitane monoalkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyethyleneimines and other customary non-ionic agents. Addition products of 30 mols ethyleneoxide and p-n-nonylphenol or propylene glycol having -80 mol percent of ethylene oxide are preferred.
• suitable protective colloids which must be added to the dispersion to increase the stability are: polyvinyl alcohol and water-soluble derivatives of polyvinyl alcohol (for example products in which about 5 percent of hydroxyl groups are acetalised, say with butyraldehyde, or in which about 10 percent of the hydroxyl groups are esterified, say with acetic acid), (compare Ullmanns Enzyklopadie der techn. Chemie, 1962, Vol. 14, pages 236-241), and cellulose ethers which are soluble in boiling water (compare Ullmanns Enzyklopadie der techn. Chemie, 1962, Vol. 5, page 171), which can be used conjointly as a constituent.
• Polyvinyl alcohol being saponified for 88 mol percent and having a polymerization degree of l,00O-l,500 and hydroxy ethyl cellulose are preferred.
• the dispersions manufactured according to the invention can be employed in all fields of use of conventional phenolic resisn or phenolic resin solutions and offer, in these fields, additional technical and commercial advantages through avoiding inflammable and/or toxic solvents and through the low contact of unreacted volatile starting compounds.
• the following may be mentioned as examples of fields of use: binders for aqueous lacquers and coating agents, binders for the manufacture of mineral wool slabs, hard papers and hard fabrics, based on cotton or glass fabrics, for decorative and electronic purposes, battery separators, air filter papers and oil filter papers for motor vehicles,
• abrasives such as emery paper, emery cloth and emery discs, curable moulding materials for the manufacture of cured shaped articles, such as, for example, brake linings, and binders for materials based on timber, such as plywood, chipboard and hardboard.
• EXAMPLE 1 396 g of aor B-phenylethylphenol, 188 g of phenol, 352 g of 44 percent strength by weight of aqueous formaldehyde solution, 30 g of 25 percent strength by weight ammonia water and 80 g of an 80 percent strength by weight aqueous solution of a polyethylene glycol ether of nonylphenol containing 30 mols of ethylene oxide reacted per mol of nonylphenol, are kept at the boil under reflux until the B-time is 7 minutes at 160C.
• Dis ersion according 6 The procedure indicated in Example 1 is followed but the phenols employed are 198 g of w or ,B-phenylethylphenol and 272 g of phenol.
• the dispersion thus obtained shows a higher curing speed than the dispersion obtained according to Example 1.
• EXAMPLE 4 The procedure according to Example 1 is retained; instead of the g of 80 percent by weight aqueous solution of the polyethylene glycol ether of nonylphenol, 64 g of a polyethylene glycol ester of colophony which contains 35 mols of reacted ethylene oxide per mol of colophony, are employed in the present case. This dispersion is distinguished by faster physical drying than that obtained according to Example 1.
• EXAMPLE 5 The procedure indicated in Example 1 is followed; instead of the 352 g of 44 percent strength by weight aqueous formaldehyde solution, only 300 g are employed.
• the dispersion thus obtained is distinguished, relative to the dispersion obtained according to Example 1, by increased flexibility of the hard papers obtained therewith.
• Example 6 The instructions of Example 1 are followed but instead of the 30 g of the polyvinyl alcohol saponified to 88 mol percent, only 20 g are used, and instead of the 10 g of hydroxyethyl cellulose 15 g are not employed. The dispersion thus obtained is distinguished by increased stability.
• EXAMPLE 8 The instructions of Example 1 are followed but instead of the 396 g of aor B-phenylethylphenol an equivalent amount of a or B-rnethylphenylethylphenol is employed. The dispersions thus obtained are distinguished by an increased physical drying speed.
• EXAMPLE 9 The instructions in Example 1 are followed but instead of the 80 g of the 80 percent strength aqueous solution of a polyethylene glycol ether of nonylphenol which contains 30 mols of ethylene oxide per mol of nonylphenol, 64 g of a polyethylene glycol ether of a polypropylene glycol which contains 80 mol per cent of reacted polyethylene oxide are employed.
• the dispersion thus obtained is distinguished by increased resistance to water and lower penetration into porous sub strates.
• Test 2 The instructions given in Test 1, are followed, however, the mixture is kept boiling under reflux whilst stirred until the B-time of the formed resin amounts to 6 minutes at 160C, before addition of further water and the 88 mol percent saponified polyvinyl alcohol having a polymerization degree of 1,000 and before addition of 80 percent strength by weight aqueous solution of a polyethylene glycol ether of nonylphenol containing 30 mols'ethylene oxide per mol nonylphenol.
• the reactionproduct is a dispersion of the type water-in-oil being not dilutable with water and having a viscosity of over 100,000 cP.
• Test 3 g The instructions given in Test 1 are followed. However, instead of the 80 g of an 80 percent strength by weight aqueous solution of a polyethylene glycol ether of nonylphenol containing 30 mols. of ethylene oxide per mol of nonylphenol, in this test 50 g ofa 50 percent strength by weight aqueous solution of the sodium salt of the half ester of sulfuric acid and polyethylene glycol ether of nonylphenol, containing 30 mols ethyleneoxide per mol nonylphenol are added.
• the obtained dispersion of the type oil-in-water can be diluted with any amounts of water.
• arylsubstituted phenols having an aromatic ring in the substituent are employed, such components are preferred which are, dissolved in phenol or substituted phenol, produced in a novel production step.
• the arylsubstituted phenol is made in a dissolved state by reacting 1 mol of phenol or substituted phenol respectively, individually orin mixture, and 1 mol of styrene or styrene derivative in-excess phenol or substituted phenol respectively, individually or in mixture, as the solvent,
• this working method is characterized in that about 2 5 percent by weight of oxalic acid, preferably 2.5 -'3.5 percent by weight oxalic acid, relative to the total weight of phenol or substituted phenol respectively, and styrene or styrene derivative respectively, are employed and the mixture is heated to 150 160C for so long until at least 95 percent by weight ofthe employed styrene or styrenederivative is present in reacted form.
• the solution being such obtained has the great advantage of being rather light-colored, nearly free of byproducts and is suitable for the manufacture of dispersions of the present invention directly without any washing and distilling procedures.
• Phenol Substituted phenol Styrene or styrene derivative Phenol Styrene or styrene derivative having ⁇ carbon respectively atoms in the ring which are reactive phenol 60-90 mol percent styrene 10-40 mol percent Wlth formaldehyde phenol 60-90 mol percent a-methylstyrene 10-40 mol percent phenol 60-90 mol percent technical vinyltoluene phenol m-cresol styrene (phenol and m-cresol giving together 60-90 mol percent) 10-40 mol percent phenol 60-90 mol percent p-bromostyrene 10-40 mol percent phenol m-pentadecenylphenol (phenol and m-penta- Further examples for mixtures (B), being obtained ecenylphenol according to the oxalic acid method from the followm g $613?
• igfi g components phenol m-cresol (phenol and m-cresol giving together 1 -90 mol percent) Substituted phenol having Styrene or styrene derivative phenol 35 dimethylphenol 3 carbon atoms in the ring respectively (phenol and 3 5 being reactive with meth lpheml giving fvrmldshyde together 60-90 mol ,0 percent) 10-40 mol percent SI rene 10-40 mol percent ot-methylstyrene 10-40 mol percent technical vinyltoluene 10-40 mol percent m-crcsol 60-90 mol percent m-crusol 00-90 mol percent m-pcnlatlccylphcnol 60-90 mol percent m-crcsol and m-pentadecylphenol giving together 60-90 mnl percent styrene 10-40 mol percent technical vinyltoluene 10-40 mol percent sty
• a mixture (A) consisting of: one or more substituted phenols which contain, as substituents, alkyl radicals with l-30 C atoms, cycloalkyl radicals with -10 C atoms which can be of monocyclic or bicyclic structure, alkenyl radicals with 1-30 C atoms and/or cycloalkenyl radicals with 5-10 C atoms, which are again of monocyclic or bicyclic structure, halogen-substituted phenols and aryl-substituted phenols having an aromatic ring in the substituent, and which have at least one but no
• phenol a mixture (B) consisting of: one or more substituted phenols which contain, as substituents alkyl radicals with l-30 C atoms, cycloalkyl radicals with 5-10 C atoms which can be of monocyclic or bicyclic structure, alkenyl radicals with 1-30 C atoms and/or cycloalkenyl radicals with 5-10 C atoms, which are again of monocyclic or bicyclic structure, halogen-substituted phenols having an aromatic ring in the substituent, and which have at least one but no morethan two carbon atoms.
• the phenolic ring being reactive with formaldehyde, with the condition that the speed of reaction of the substituted phenol with formaldehyde is 40 to 150 percent of the speed of reaction of the unsubstituted phenol, and
• a mixture (C) consisting of: one or more substituted phenols which contain, as substituents, alkyl radicals with 1-30 C atoms, cycloalkyl radicals with 5-10 C atoms which can be of monocyclic or bicyclic structure, alkenyl radicals with l-30 C atoms and/or cycloalkenyl radicals with 5-10 C atoms, which are again of monocyclic or bicyclic structure, halogen-substituted phenols and arylsubstituted phenols having an aromatic ring in the substituent, and which have at least one but no more than two carbon atoms in the phenolic ring being reactive with formaldehyde, with the condition that the speed of reaction of the substituted phenol with formaldehyde is 40 to 150 percent of the speed of reaction of the unsubstituted, phenol, and
• phenol 5 and one or more other substituted phenols which contain, as substituents, alkyl radicals with l-30 C atoms.
• cycloalkyl radicals with 5-10 C atoms which can be of monocyclic or bicyclic structure, alkenyl radicals with l-30 C atoms and/or cycloalkenyl radicals with 5-10 C atoms, which are again of monocyclic or bicyclic structure, halogen-substituted phenols and aryl-substituted phenols having an aromatic ring in the substituent, and which have three carbon atoms in the phenolic ring which are reactive with formaldehyde, with the condition that the speed of reaction of the substituted phenol with formaldehyde is 40 to 150 percent of the speed of reaction of'the unsubstituted phenol, is mixed with formaldehyde or formaldehyde donors and basic nitrogen compounds, selected from the group consisting of ammonia and/or primary or secondary amines,
• the second step mixed with water and protec tive colloid and agitated mechanically until a phase inversion of the dispersion takes place, so that a dispersion of the oil-in-water type is present, and the phenolic resin-in-water-type dispersion is further condensed, by warming, until a sample of the dispersion, when withdrawn, has a curing-time of 30 seconds up to 10 minutes at 160C, and thereafter the batch is cooled whilst stirring.
• phenol is made by reacting 1 mol of phenol with 1 mol of styrene or styrene derivative selected from the group consisting of a-methyl styrene, vinyl toluene and p-bromo styrene in excess phenol as the solvent, whereby about 2 to 5 percent by weight of oxalic acid are employed, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative, respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least 95 percent by weight of the styrene or styrene derivative employed is present in reacted form, or
• a mixture (B) consisting of: one or more substituted phenols having at least one but no more than two carbon atoms in the phenolic ring which are reactive with formaldehyde, and
• one or more other substituted phenols having 3 carbon atoms in the ring which are reactive with formaldehyde is made by reacting 1 mol of phenol with 1 mol of styrene or styrene derivative selected from the group consisting of a-methyl styrene, vinyl toluene and p-bromo styrene in excess phenol as the solvent, whereby about 2 to 5 percent by weight of oxalic acid are employed, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative, respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least 95 percent by weight of the styrene or styrene derivative employed is present in reacted form, or
• a mixture (C) consisting of: one or more substituted phenols having at least one but no more than two carbon atoms in the phenolic ring which are reactive with formaldehyde, and
• phenol is made by reacting 1 mol of phenol with 1 mol of styrene or styrene derivative selected from the group consisting of a-methyl stryene, vinyl toluene and p-bromo styrene in excess phenol as the solvent, whereby about 2 to 5 percent by weight of oxalic acid are employed, preferably 2.5 to 3.5 percent by weight, relative to the total amount of phenol and styrene or styrene derivative, respectively, by heating in one step to about 150 to 160C and kept at this temperature until at least 95 percent by weight of the styrene or styrene derivative em ployed is present in reacted form, and
• the mixture A, B or C is reacted with formaldehyde or formaldehyde donors and basic nitrogen compounds selected from the group consisting of ammonia and/or primary or secondary amines, whereby the mixture A, B or C is employed in such amounts that the average functionality ofthe sum of these phenolic compounds of the mixture A, B or C to formaldehyde is between 2.1 and 2.8 and the amount of formaldehyde is so chosen that the molar ratio of the total sum of added formaldehyde to the sum of phenolic compounds in the mixture A, B or C is between 0.9 and 15:1 and wherein the basic nitrogen compound being employed in amounts of 5 to 50 mol percent, relative to the total weight of phenolic compounds in the mixture A, B or C, by warming at the boil under reflux until a sample of the condensation product withdrawn has a curing-time of 6 15 minutes at 160C, then the batch is cooled to below C and in the third step: The resulting water-in-phenolic resin dispersion of

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• 1972
  • 1972-06-19 CH CH919772A patent/CH569681A5/xx not_active IP Right Cessation
• 1973
  • 1973-06-15 CA CA174,121A patent/CA1010172A/en not_active Expired
  • 1973-06-15 CA CA174,117A patent/CA1013086A/en not_active Expired
  • 1973-06-16 DE DE2330815A patent/DE2330815A1/de active Pending
  • 1973-06-16 DE DE2330816A patent/DE2330816C3/de not_active Expired
  • 1973-06-16 DE DE19732330851 patent/DE2330851B2/de not_active Ceased
  • 1973-06-16 DE DE2330849A patent/DE2330849A1/de active Pending
  • 1973-06-16 DE DE2330850A patent/DE2330850B2/de not_active Withdrawn
  • 1973-06-18 US US370771A patent/US3875089A/en not_active Expired - Lifetime
  • 1973-06-18 AT AT535273A patent/AT329872B/de active
  • 1973-06-18 US US370768A patent/US3878136A/en not_active Expired - Lifetime
  • 1973-06-18 US US370962A patent/US3870670A/en not_active Expired - Lifetime
  • 1973-06-18 AT AT532073A patent/AT329870B/de not_active IP Right Cessation
  • 1973-06-19 GB GB2901873A patent/GB1423446A/en not_active Expired
  • 1973-06-19 GB GB2902073A patent/GB1422410A/en not_active Expired
  • 1973-06-19 BE BE132435A patent/BE801118A/xx unknown
  • 1973-06-19 FR FR7323582A patent/FR2189457B1/fr not_active Expired
  • 1973-06-19 FR FR7323581A patent/FR2189357B1/fr not_active Expired
  • 1973-06-19 FR FR7323580A patent/FR2219199B1/fr not_active Expired
  • 1973-06-19 GB GB2902173A patent/GB1422883A/en not_active Expired
  • 1973-06-19 BE BE132437A patent/BE801120A/xx unknown
  • 1973-06-19 BE BE132436A patent/BE801119A/xx unknown
  • 1973-06-19 BE BE132433A patent/BE801116A/xx unknown
  • 1973-06-19 FR FR7323583A patent/FR2189458B1/fr not_active Expired
  • 1973-06-19 NL NL7308484A patent/NL7308484A/xx unknown
  • 1973-06-19 NL NL7308486A patent/NL7308486A/xx unknown
  • 1973-06-19 NL NL7308489A patent/NL7308489A/xx unknown
  • 1973-06-19 GB GB2902273A patent/GB1406944A/en not_active Expired

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